CN1894080A - 造粒方法 - Google Patents
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Abstract
本发明包含用于热塑性可挤出树脂组合物造粒的成形方法。所述树脂组合物含有热塑性聚合物、增塑剂和备选的其它添加剂。所述增塑剂含有在室温下为固体的组分。所述方法在高于增塑剂的熔点但低于热塑性聚合物的熔化/塑化温度的温度进行。
Description
技术领域
本发明涉及热塑性可挤出聚合物的造粒方法。
背景技术
在塑料工业中,热塑性可挤出聚合物的造粒方法是众所周知的。一般而言,粒料为圆柱形,其直径约3mm,长度约3mm。很多种塑料制品的制作方法中均采用粒料。
造粒方法一般包括塑化步骤。在该步骤中,将待造粒的配料熔化并喂入双螺杆挤出机中。这种做法被认为是有益的,因为已经发现,由于在挤出机中所有熔化组分均得到有效混合,从而所制得的粒料由粒料组分的均匀混合物组成。
EP-A-0 415 357描述了通过熔融挤出制作含有聚乙烯醇(PVOH)的粒料的方法,其中的挤出在150~195℃的温度范围内进行。
具有塑化步骤的造粒方法有与其相关的多个缺点。其中主要的缺点是需要加热,这意味着这类方法的能耗很高。
此外,这类“热”法不适用于具有热敏性的聚合物(如聚乙烯醇),因为此类物质在受热时会发生降解。而且,这类“热”法使聚合物经历了受热过程,已经发现这会对聚合物的性质产生不利影响。对于聚乙烯醇,已经发现受热过程对聚乙烯醇的水溶性有十分有害的影响。
在其它造粒方法中,在低温下对粒料组分进行干压。由此避免了上述“热”法的缺陷。
WO-A-98/26911描述了一种制作聚乙烯醇粒料的低温方法。在该方法中,粒料成分(此处为粉末状聚乙烯醇和诸如增塑剂等各种添加剂的混合物)被送入两个滚筒之间而被压缩成粒料。由于粒料混合物中的聚乙烯醇成分在该方法中未被熔化,因此避免了热降解问题。
此外,GB-937 057描述了这样一种低温压缩方法。首先在高温下混合增塑剂和聚乙烯醇之后进行该低温压缩方法。
然而,尽管该方法(冷压缩方法)消除了聚合物的热致降解问题,但是所制作的粒料还存在其它缺陷。
这些缺陷大多源于压缩方法的固有性质,更具体地讲,源于滚筒和其中的粉末喂料。已经发现,很难保证将粉末喂料在滚筒上均匀散布。其结果是很难控制粒料的大小,因此,粒料尺寸会有很大的差异。
而且,这种方法一般会形成很多粉尘。另外,由于这种粒料通常易碎,完整性差,在相互摩擦的过程中很容易形成粉尘,从而加剧了起尘问题。这两个问题均归因于不佳的散布和滚筒压缩技术。
另外,还发现该粒料的组成差异显著,均质性差。相信这些问题也与粉末在滚筒上分布不匀有关。当该粒料被用于随后的加工步骤时,粒料组成的变化性及均质性差的问题将会加剧。
这些种类的粒料(其中,粒料的热塑性聚合物组分是聚乙烯醇)被用来通过挤出/注射成型法制作水溶性聚乙烯醇袋。例如,这种袋子一般用来容纳用在自动洗涤机(洗衣机或洗碗机)中的洗涤剂组合物。在这些用途中,粒料必需具有高度的均一性,以保证所制作的袋子具有良好的完整性,从而在贮存中稳定,并具有预期的水溶性。
如前所述,利用冷压缩方法制作的粒料通常无法满足制作袋子所需的均质性。
发明内容
本发明的一个目的是消除或缓解上面所列的问题。
本发明提供了用于热塑性可挤出树脂组合物造粒的成形方法,所述树脂组合物含有热塑性聚合物、增塑剂和备选的其它添加剂,所述增塑剂含有室温下为固体的组分,其中,所述方法在高于所述增塑剂的熔点但低于所述热塑性聚合物的熔化/塑化温度的温度进行。
所述成形方法可包括压制、挤出、压延和/或压实。最优选该成形方法包括挤出。
已经发现本发明的方法克服了现有技术的缺点。首先,由于该方法在低于热塑性聚合物的熔化/塑化温度的温度进行,因此发现该方法非常节能。另外,由于在低温下加工,所以树脂混合物中热敏性物质的热降解大大减少。
另外,由于该方法在增塑剂的熔点以上进行(之后使之冷却以形成固体粒料),所以粒料的易碎性很低。因此,这种粒料因摩擦而释放粉尘的可能性很小。
而且,由于粒料在增塑剂成分的熔点以上的温度制作,因此发现其具有优异的均质性。更具体地讲,发现每颗粒料的总体组成和粒料内各个组分的分布都具有高度的可预测性,而且其偏差很小。当粒料用于诸如二次挤出加工(如,注射成型)等进一步加工步骤中以制作含有热塑性聚合物的塑料物品时,这种性质尤其重要。
具体实施方式
通常,组分以颗粒形式输送到该方法中所使用的成形设备中。
已经发现,用于制作粒料的原料的颗粒尺寸应该较小。这是为了保证粒料具有高的均质性。所用原料的颗粒尺寸优选小于2000μm,更优选小于1200μm,更优选小于400μm,最优选约200μm。
组合物中增塑剂的含量至少为5%,更优选10%,最优选15%。
在任何时候,挤出机中原料的温度优选不超过热塑性聚合物熔化/塑化温度以下10℃的温度。更优选该温度不超过热塑性聚合物的熔化/塑化温度以下15℃的温度,更优选不超过热塑性聚合物的熔化/塑化温度以下30℃的温度,最优选不超过热塑性聚合物的熔化/塑化温度以下45℃的温度。然而,理想的是,原料的温度高于环境空气的温度。挤出机中原料的温度优选为至少40℃,更优选至少45℃,最优选至少50℃。
在优选的操作温度下,增塑剂必须至少部分熔化。增塑剂组分的熔点优选比热塑性聚合物的熔化/塑化温度低至少15℃,更优选比热塑性聚合物的熔化/塑化温度低至少30℃,最优选比热塑性聚合物的熔化/塑化温度低至少45℃。
增塑剂优选含有碳水化合物。
碳水化合物通常由通式Cx(H2O)y表示。此处的术语也涵盖了性质上与碳水化合物类似的物质,例如葡萄糖酸或氨基糖,它们不能完全用该通式来表示。该术语包括例如糖醇等其他碳水化合物的衍生物,所述糖醇有例如山梨糖醇、葡萄糖醇、甘露醇、半乳糖醇、卫矛醇、木糖醇、赤藓糖醇、异麦芽糖(isomaltutose)及异麦芽酮糖醇(isomalt)等。
最优选的碳水化合物包括热稳定性更高的碳水化合物,如山梨糖醇、葡萄糖醇、甘露醇、半乳糖醇、卫矛醇、木糖醇、赤藓糖醇、异麦芽糖及异麦芽酮糖醇。
其它优选的增塑剂体系包括固体脂肪酸烷氧基酯、脂肪醇烷氧基酯或聚亚烷基二醇(例如长链聚乙二醇)。
增塑剂还可以包含辅助成分。优选的辅助成分包括甘油、乙二醇、丙二醇、二甘醇、二乙二醇、二丙二醇、三乙醇胺、二乙醇胺和甲基二乙胺等。
特定的线材或每股线材一旦从挤出机中挤出,可以使之在环境状况下自然冷却。另外,也可以辅助冷却。这样做的一种方法是,采用冷金属带,将特定的线材或每股线材挤出到该金属带上。这样做的另一种方法是,在挤出机的下游采用冷流体,优选冷空气。还有一种方法是沿特定的线材或每股线材的横向吹送流体,优选吹风。可以采用上述方法的一种或几种。
在制作过程中,优选将特定的线材或每股线材断裂成粒料。
优选通过切割的方式将该线材断裂成粒料。不过,也不排除其它断裂方法,如绞扭法。可以考虑这样的方法:趁线材尚具塑性时,以一定间隔对其进行绞扭,从而形成一串“香肠”,连结处一旦变得更脆,即可将其断开。还可以通过局部切割、挤压、夹压或打孔(所有这些方法在此总称为“刻痕”)形成可发生脆性断裂的“蹼(web)”,从而形成粒料前体。可以在制造过程中或由消费者使粒料前体断裂而形成粒料,所提供的前体具有可操作的长度,消费者根据需要从其上断开或扭下粒料。例如,粒料的前体可以是直排粒料,可以按需要断开。
挤出压力可以是以有效方式实施该方法的任何压力。比较适宜的压力是大于3巴(0.3兆帕),优选大于5巴(0.5兆帕),更优选大于8巴(0.8兆帕)。更优选大于12巴(1.2兆帕)。最优选大于40巴(4兆帕)。不过,挤出压力优选不超过100巴(10兆帕),更优选不超过60巴(6兆帕)。
一般而言,粒料在注射成型方法中使用。优选采用注射成型方法来制造水溶性小袋,这种小袋用来容纳自动洗衣机或自动洗碗机中所用的洗涤制剂。因此,粒料优选含有水溶性或水分散性热塑性聚合物。
已经发现,在这一应用中,按照本发明所制作的粒料的有利性质(特别是高均质性)非常有益。据信该性质最为有益,因为注射成型产品的完整性依赖于被注射成型组合物的这种高度的均质性,否则,低均质性会反映在注射成型的产品中。已经发现,高均质性可以使注射成型的产品具有可预测的水溶性。
水溶性/水分散性热塑性聚合物优选含有聚乙烯醇或其衍生物。
在该方法中可以采用其它水溶性/水分散性聚合物来替代聚乙烯醇,或与聚乙烯醇一同使用。优选的例子有聚乙烯吡咯烷酮、聚丙烯酸、聚马来酸、纤维素衍生物(如纤维素醚或羟丙基甲基纤维素)、聚乙交酯、聚乙醇酸、聚丙交酯、聚乳酸及其共聚物。
被加工的混合物中可以含有加工助剂。优选的加工助剂包括一元羧酸、二元羧酸、三元羧酸或其盐、如硬脂酸等脂肪酸或其盐、单酸甘油酯、二酸甘油酯、三酸甘油酯或其盐、气相二氧化硅(aerosil)、无机颜料和有机颜料。
现在,参考下面的非限定性实施例来阐明本发明。
实施例
实施例1:
在挤出机(双螺杆挤出机,由意大利米兰的ICMA S.Giorgio公司制造,该公司致力于塑料共混物和塑料合金的加工)中进行造粒。
挤出机具有如下特性:
螺杆直径:35mm
螺杆长度:40cm
加工压力:30bar(巴)
输出:5kg/h.(千克/小时)
温度区域:6(T1=50℃,T2=60℃,T3=T4=90℃,T5=105℃以及
T6(口模)=105℃)
挤出机与作为冷却源的双辊设备连接,并且连接到粒料切割机上。
将下面的粉末状配料喂入挤出机中:
原料 | % |
聚乙烯醇树脂 | 85.0 |
山梨醇 | 11.0 |
加工助剂 | 4.0 |
合计 | 100.0 |
将所得到的粒料冷却到室温。利用此配料得到的固体粒料具有低的脆性。
实施例2:
在颗粒压制机(Universal Milling Technologies的V3-75型)上进行造粒。
该压制机具有如下特性:
口模直径:350mm
孔直径:2mm
孔长度:3mm
料斗:45°
口模/滚筒间距:1.5mm
口模速度:5m/s(米/秒)
电动机:30kW
温度:98~102℃
将下面粉末状配料喂入压制机中:
原料 | 配料1 | 配料2 | 配料3 |
聚乙烯醇树脂 | 81.0 | 87.0 | 85.0 |
山梨醇 | 15.0 | 11.0 | 11.0 |
加工助剂 | 4.0 | 2.0 | 4.0 |
合计 | 100.0 | 100.0 | 100.0 |
将所得到的粒料冷却到室温。每种配料所得到的固体粒料具有低的脆性。
Claims (15)
1.用于热塑性可挤出树脂组合物造粒的成形方法,所述树脂组合物含有热塑性聚合物、增塑剂和备选的其它添加剂,所述增塑剂含有室温下为固体的组分,其中,所述方法在高于所述增塑剂的熔点但低于所述热塑性聚合物的熔化/塑化温度的温度进行。
2.如权利要求1所述的方法,其中,所述方法包括压制、挤出、压延和/或压实。
3.如权利要求1或2所述的方法,其中,所述组合物中的增塑剂含量为至少5%,优选10%,最优选15%。
4.如权利要求2或3所述的方法,其中,所述成形方法包括挤出。
5.如权利要求4所述的方法,其中,在任何时候,挤出机中原料的温度不超过热塑性聚合物熔化/塑化温度以下10℃的温度,更优选不超过热塑性聚合物的熔化/塑化温度以下15℃的温度,更优选不超过热塑性聚合物的熔化/塑化温度以下30℃的温度,最优选不超过热塑性聚合物的熔化/塑化温度以下45℃的温度。
6.如权利要求4或5所述的方法,其中,挤出机中原料的温度为至少40℃,更优选至少45℃,最优选至少50℃。
7.如前述任一项权利要求所述的方法,其中,所用原料的颗粒尺寸小于2000μm,更优选小于1200μm,更优选小于400μm,最优选约200μm。
8.如权利要求1~7任一项所述的方法,其中,所述增塑剂含有碳水化合物。
9.如权利要求8所述的方法,其中,所述碳水化合物选自包括葡萄糖酸、氨基糖以及例如山梨糖醇、葡萄糖醇、甘露醇、半乳糖醇、卫矛醇、木糖醇、赤藓糖醇、异麦芽糖及异麦芽酮糖醇等糖醇的组。
10.如权利要求8所述的方法,其中,所述碳水化合物选自包括山梨糖醇、葡萄糖醇、甘露醇、半乳糖醇、卫矛醇、木糖醇、赤藓糖醇、异麦芽糖及异麦芽酮糖醇的组。
11.如权利要求1~10任一项所述的方法,其中,所述热塑性聚合物是水溶性的或水分散性的。
12.如权利要求11所述的方法,其中,所述热塑性聚合物含有聚乙烯醇或其衍生物。
13.如权利要求1~12任一项所述的方法,其中,所述热塑性聚合物包含聚乙烯吡咯烷酮、聚丙烯酸、聚马来酸、纤维素衍生物(如纤维素醚或羟丙基甲基纤维素)、聚乙交酯、聚乙醇酸、聚丙交酯、聚乳酸及其共聚物。
14.如权利要求12或13所述的方法,其中,所得粒料用于注射成型加工。
15.如权利要求12~14任一项所述的方法,其中,所述注射成型方法用来制造水溶性小袋,这种小袋用来容纳自动洗衣机或自动洗碗机中所用的洗涤制剂。
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GB0329529.2 | 2003-12-19 | ||
GB0329529A GB2409204A (en) | 2003-12-19 | 2003-12-19 | Plasticized thermoplastic polymer |
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CN1894080A true CN1894080A (zh) | 2007-01-10 |
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US (3) | US20070075453A1 (zh) |
EP (2) | EP1694480B1 (zh) |
CN (1) | CN1894080A (zh) |
AU (2) | AU2004299333B2 (zh) |
BR (1) | BRPI0416904A (zh) |
CA (1) | CA2549149C (zh) |
ES (1) | ES2536277T3 (zh) |
GB (1) | GB2409204A (zh) |
PL (2) | PL2202040T3 (zh) |
TR (1) | TR201900584T4 (zh) |
WO (1) | WO2005058569A1 (zh) |
ZA (1) | ZA200604239B (zh) |
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CN101878099B (zh) * | 2007-09-28 | 2013-06-05 | 水溶性塑料制品有限公司 | 制备高流动性聚乙烯醇小球的方法及聚乙烯醇小球 |
CN107802041A (zh) * | 2017-11-28 | 2018-03-16 | 广东汇星新材料科技股份有限公司 | 一种可长期去除体味的内衣 |
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US20110248423A1 (en) * | 2010-04-07 | 2011-10-13 | Steven Proper | Synthetic Mulch and Method of Making Same |
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2003
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2004
- 2004-12-16 BR BRPI0416904-2A patent/BRPI0416904A/pt not_active Application Discontinuation
- 2004-12-16 CN CNA200480037456XA patent/CN1894080A/zh active Pending
- 2004-12-16 ES ES10158305.2T patent/ES2536277T3/es active Active
- 2004-12-16 CA CA2549149A patent/CA2549149C/en not_active Expired - Fee Related
- 2004-12-16 AU AU2004299333A patent/AU2004299333B2/en not_active Ceased
- 2004-12-16 EP EP04806087.5A patent/EP1694480B1/en active Active
- 2004-12-16 WO PCT/GB2004/005273 patent/WO2005058569A1/en active Application Filing
- 2004-12-16 PL PL10158305T patent/PL2202040T3/pl unknown
- 2004-12-16 TR TR2019/00584T patent/TR201900584T4/tr unknown
- 2004-12-16 US US10/595,919 patent/US20070075453A1/en not_active Abandoned
- 2004-12-16 EP EP10158305.2A patent/EP2202040B1/en active Active
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101878099B (zh) * | 2007-09-28 | 2013-06-05 | 水溶性塑料制品有限公司 | 制备高流动性聚乙烯醇小球的方法及聚乙烯醇小球 |
CN107802041A (zh) * | 2017-11-28 | 2018-03-16 | 广东汇星新材料科技股份有限公司 | 一种可长期去除体味的内衣 |
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EP2202040B1 (en) | 2015-02-25 |
AU2004299333A1 (en) | 2005-06-30 |
BRPI0416904A (pt) | 2007-01-16 |
EP1694480B1 (en) | 2018-10-24 |
TR201900584T4 (tr) | 2019-02-21 |
AU2010212479A1 (en) | 2010-09-09 |
CA2549149A1 (en) | 2005-06-30 |
US9327425B2 (en) | 2016-05-03 |
ES2536277T3 (es) | 2015-05-22 |
AU2010212479B2 (en) | 2012-03-01 |
CA2549149C (en) | 2015-08-25 |
WO2005058569A1 (en) | 2005-06-30 |
EP1694480A1 (en) | 2006-08-30 |
ZA200604239B (en) | 2007-10-31 |
US20110062620A1 (en) | 2011-03-17 |
EP2202040A2 (en) | 2010-06-30 |
US20070075453A1 (en) | 2007-04-05 |
EP2202040A3 (en) | 2013-02-20 |
US20160279830A1 (en) | 2016-09-29 |
PL1694480T3 (pl) | 2019-05-31 |
PL2202040T3 (pl) | 2015-07-31 |
GB0329529D0 (en) | 2004-01-28 |
GB2409204A (en) | 2005-06-22 |
AU2004299333B2 (en) | 2010-06-17 |
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